Coordination compounds containing trivalent phosphorus compounds and certain metal compounds



United States Patent Int. Cl. c01 1/00 ULS. (:1. 23-190 21 Claims Thisapplication is a continuation-in-part of application Ser. No. 47,904,filed Aug. '8, 1960, now abandoned.

This invention relates to novel materials suitable for use astrocketpropellants and jet fuels and as additives for use in these and alliedfields. More particularly, the invention relates to solid and liquidrocket propellants; and liquid jet and internal combustion engine fuelsand additives, and to methods for the preparation thereof.

While propellant fuels employed heretofore have produced an effectivepropulsive force when employed in jet and rocket engines, many compoundsknown to be capable of releasing significantly greater amounts of energyper unit and thus capable of effecting markedly enhanced propulsion whenemployed as fuels, have failed of general acceptance due to certaindifiiculties inherent therein. Illustrative of these compounds are thehydrides of boron, aluminum, beryllium, and the like. The principaldisadvantages of these compounds have been their high cost and theirdifliculty in handling during manufacture,.transportation, storage, anduse. These compounds have also evidenced a very marked hydrolytic andpyrolytic instability requiring the complete exclusion of even thesmallest traces of water and atmospheric oxygen from their presence.Further, these compounds are highly toxic in nature.

We have now discovered, however, compounds which are capable ofeffecting a propulsive force in rocket and jet engines approximatelyequivalent to that of the hydridesabove referred to while avoidingsubstantially the difficulties inherent therein and alluded to above. Asignificant advantage of the propellant compounds of the presentinvention is the reduction in maximum flame temperature achieved therebywithout diminution or loss of impulse thrust when employed in jet androcket engines. These compounds also provide, as indicated above,valuable additives for use in jet and internal combustion engrnes.

Thus, the present invention involves the stabilization of metal hydridesand organometallic compounds by means of coordination between electrondonor and electron acceptor molecules. For the preparation of highenergy fuels by the practice described herein, the electron donorcompounds comprise nitrogen and phosphorus containing compounds whereinthe nitrogen and phosphorus moieties are in the trivalent state.Accordingly, and more elaborately, the compounds of the invention aretherefore coordination complexes formed by virtue of a suitable electrondonor-electron acceptor relation found to exist between trivalentphosphorus and nitrogen donor compounds, e.g. phosphine, mono-, diandtri-aryl, alkyl and nitro phosphines, nitroalkyl, alkylene and alkenyl(e.g. vinyl) phosphines, nitrated derivatives of phosphines and alkylphosphines, ammonia, mono-, diand tri-alkyl, aryl, alkenyl andnitroalkyl amines, alkyl alkylene imines, alkylene i imines (e.g.,ethylene imine), polyamines, (e.g. alkylene diamines, such as ethylenediamine), hydrazine, monoand di-alkyl hydrazines (e.g. dimethylhydrazine), aniline, alkenyl, alkyl and aryl nitriles (e.g.acrylonitrile), and. the electronacceptor compounds, that is, beryllium,

3,512,932 Patented May 19, 1970 ice lithium, magnesium, sodium, calcium,aluminum, potassium, silicon and boron hydrides, and the correspondingborohydrides and alkyl organometallic compounds of the aforesaid metals.These coordination complexes thus provide that compounds capable of highenergy release upon combustion, which were, however, unsuitable for useas propulsion agents in rockets or jet engines hitherto because of theirhydrolytic and/ or pyrolytic instability, are now made sufficientlystable to permit the use of conventional handling techniques inmanufacture, transportation, storage, use, and the like, thus permittingtheir employment as propulsive agents in high energy fuels.

It is noted that the terms alkyl, alkylene, and alkenyl as employedherein are intended preferably to en compass the corresponding lowerhydrocarbons wherein the number of carbon atoms is from 1 to 6 and mostdesirably from 1 to 3.

Thus, the novel metal hydride coordination compounds of the inventionmay be represented by the formulae: M-(X) and Y-(Z) wherein M isberyllium hydride, BeH lithium hydride, LiH; magnesium hydride, Mgl-ialuminum hydride, AlH lithium-aluminum hydride, LiAlH berylliumborohydride, Be(BI-I lithium borohydride, LiBH aluminum borohydride,AI(BH or magnesium borohydride, Mg(BH.,) as well as aluminum berylliumhydride, lithium beryllium hydride, magnesium berylium hydride, sodiumborohydride, potassium borohydride and calcium borohydride; X is analkylene (e.g. ethylene) phosphine,

n bowl: Hz

alkenyl (e.g. vinyl) phosphine, H PCH =CH an alkyl nitrate phosphine,such as methyl nitrate phosphine where in the methyl nitratesubstituents are within the range of 1 to 3; thus, mono-(methylnitrate)-phosphine, H PCH NO di(methyl nitrate) phosphine, HP- CH NOtri- (nitro-methyl) phosphine, P [CH (NO tri(methyl nitrate) phosphine,P(CH NO a phosphine nitrate, or a monoor di-nitro substituted phosphine,i.e., H PNO HP(NO phosphine, PH a mono-dior tri-alkyl or aryl phosphine,PR wherein R is an alkyl, aryl or nitro-substituted alkyl; ammonia, NHa. mono-, dior tri-alkyl, nitro alkyl or aryl amine, NH R(3 wherein Rretains the same value as recited above; as well as an alkylene imine,alkyl alkylene imine, polyamine (e.g., hexamethylenetetramine, analkylene diamine such as ethylene diamine), hydrazine, monoor di-alkylhydrazine, aniline, or an alkenyl, alkyl or aryl nitrile; Y is one ofthe aforesaid metal hydrides or metal borohydrides or organometalliccompounds encompassed by M as recited above, or, in addition, may be aboron hydride or an alkyl derivative thereof containing within the rangeof 2 to 10 boron atoms, which boranes are encompassed by the formula,B,,R in which each of the R substituents present is a hydrogen atom oran alkyl radical; and when the latter preferably a lower alkyl radical;a.g., diborane, B H tetraborane, B H pentaborane, B H or decaborane, B HZ is phosphine; ethylene phosphine, vinyl phosphine, a methyl nitratephosphine wherein the methyl nitrate substituents at tached to thephosphorus nucleus are within the range of l to 3; a phosphine nitrate;or a nitrophosphine again, most desirably, a monoor di-nitro substitutedphosphine, as defined above; ammonia, an alkyl amine, an alkyl alkyleneamine, an alkylene imine, polyamine, hydrazine, dialkyl hydrazine,aniline or an alkenyl, alkyl or aryl nitrile; b is an integer from 1 to2 inclusive; n is an integer within the range of 1 to 10, and c iseither 4 or 6. Other suitable electron acceptor compounds for use hereininclude the silicon hydrides. Each nitro-alkyl substituent where presentcontains preferably 1 to 2 nitro groups.

Other coordination compounds, which provide valuable propellants andfuel additives for use in accordance with the invention, are includedamong the borane-phosphines described in copending application Ser. No.47,943 filed by the inventors herein on Aug. 8, 1960, now abandoned. Ofthese the borane-phosphines for use herein may be represented by thegeneral formula:

wherein each of the R substituents is a hydrogen atom or an alkylradical, preferably a lower alkyl radical; a is an integer from 2 to 10inclusive; and c is the integer 4 or 6. The expression, (1 to a), refersto the numerical value within the range of 1 to that of the integersymbolized by a as recited above; that is from 1 to 10 inclusive but notin excess of the value of a in any specific instance.

The term borane is utilized herein to encompass compounds formed of aplurality of boron atoms (i.e. 2 to 10 in number), having attachedthereto hydrogen and/ or alkyl substituents.

Illustrative of the novel hydride coordination compounds of theinvention are aluminum borohydride-phosphine, berylliumborohydride-phosphine, lithium borohydride-methyl phosphine, lithiumaluminum hydride-phosphine, aluminum borohydride-dimethyl phosphine,lithium borohydride-phosphine, beryllium hydride-ethylene phosphine,lithium hydride-mono-(methyl nitrate) phosphine, magnesiumhydride-di(methyl nitrate) phosphine, aluminum hydride-tri(nitromethyl)phosphine, magnesium borohydride-phosphine nitrate, lithium aluminumhydride-dinitrophosphine, lithium hydride-vinyl phosphine, berylliumborohydride-ethylene phosphine, diborane-vinyl phosphine,tetraborane-vinyl phosphine, tetraborane-ethylene phosphine,tetraborane-di(methylnitrate) phosphine, tetraborane-phosphine nitrate,tetraborane-dinitrophosphine, pentaborane-ethylene phosphine,decaborane-di- (methyl nitrate) phosphine, pentaborane-dinitrophosphine,lithium aluminum hydride-dimethyl amine, lithium aluminumhydride-hydrazine, aluminum borohydride-diethyl hydrazine, aluminumborohydride-monomethyl amine, aluminum borohydride-ethylene imine,aluminum borohydridehydrazine, pentaborane-ethylene imine,tetraborane-monovinyl amine, diborane-polymerized ethylene amine, andberyllium borohydride-ammonia.

Illustrative of the borane-phosphines are pentaborane-diphosphine, B H(PH decaborane-diphosphine, B H (PH pentaborane-di (trimethylphosphine BH [P (CH decaborane-di(methylphosphine) B H [H PCHtetraborane-phosphine, B H -PH and tetraborane trimethylphosphine, B H-P(CH The propellant and fuel additive coordination compounds hereindescribed are formed by admixture of a metal hydride as represented bythe symbols M and Y in the above recited formulae with a phosphineencompassed by the symbols X and Z, respectively, of the aforesaidformulae. The preparation of borane-phosphines encompassed by theformula, B R [PR' to is described in the copending application Ser. No.47,943, filed by the inventors herein on Aug. 8, 1960, now abandoned. Ingeneral, the procedure comprises reaction of boron hydrides or boranesas represented by the formula B,,R defined above, with a phosphine, PRhaving the value ascribed thereto hereinabove. The mole ratio of hydrideto phosphine in the reaction mixtures is within the range of 1:1 to 1:2respectively; and normally substantially equimolar proportions ofhydride and phosphine are utilized. The mole ratio of reactants,however, may be extended upward to 1:10, respectively. The reactionoccurs preferably at a temperature within the range of -30 C. to 50.,and takes place most desirably in the presence of a suitable organicsolvent, and particularly alkyl ethers, furans, and aliphatic andaromatic hydrocarbon solvents, such as, for example, diethyl ether,tetrahydrofuran, toluene, xylene, isooctane, and the like. The finalproducts, the coordination compounds, like the reactants, are readilysoluble in these solvents, and are indeed often incorporated in suchmedia to facilitate handling when used particularly as additives forincorporation in internal combustion and jet propulsion engine fuels.The term jet-propulsion, it should be noted, as employed throughout thisspecification and unless otherwise indicated, is intended to encompassrocket as well as jetpropulsion.

The coordination complexes are either liquids, solids, or polymerizableliquids, as where organometallic, organophosphorus or organonitrogencompounds are utilized which contain a polymerizable bond (e.g. a doublebond); for example, where the phosphine or nitrogen containingconstituent is polymerizable vinyl or ethylene phosphine, ethylene imineor allyl amine, the polymerizable compounds being capable aftercoordination of reaction to form their own solid matrices when employedas propellant fuels; these solid fuels being formed at the lowestfeasible ratio of carbon to metal hydride, thus resulting in fuelscapable of releasing substantially more energy in comparison with thestandard carbon polymer binder which is of lower energy content than thecoordination compounds containing polymerizable bonds, as referred toabove. The liquid and solid complexes can be incorporated desirablynevertheless in such standard polymer binders, e.g. a polymerizedhydrocarbon, in the practice of the invention.

The formulations of coordination compounds for use in jet or rocket fuelengines are therefore standard and assume a variety of forms. Thus, theymay be varied to produce fuels which burn spontaneously when mixed withoxidizer; ignite upon injection into a hot chamber; undergo combustionupon being heated in the presence of a suitable oxidizer; or burn bymeans of ignition from an external source. Fuel burning rate, as well asthe thrust generated, may be continuously varied under close controlwith the use of bipropellant and hybrid propellant forms. Monopropellantformulations can, of course, also be used effectively. In thebipropellant form, the fuel composition includes a liquid coordinationcompound and oxidizer, each of which is maintained separately from theother prior to use. The hybrid propellant form may be used with solidcoordination complexes in which case the fuel composition will include,prior to use, some oxidizer, but its firing rate is controlled by aseparate liquid oxidizer stream. By way of illustrating the foregoingmethods, oxygen, for example, may be introduced into the fuel disposed,in situ, within the combustion chamber and the mixture ignited from anexternal source. Liquid or solid fuel is simply combined with theoxidizer in the monopropellant formulation. The oxidizers empolyed areconventional within the field and include, as noted, liquid andatmospheric oxygen, ozone, tetranitromethane, nitrogen trifiuoride,chlorine, sodium nitrate, mixed oxides of nitrogen fluorine (gaseous),oxygen difluoride, nitrogen trifiuoride, nitrogen difluoridemonochloride, nitrogen trichloride, phosphorus nitrates, fluorine,nitric acid, ammonium perchlorate and mixed oxychlorates andperchlorates, peroxides, e.g. hydrogen peroxide, and oxonides; thesematerials being particularly well adapted to use in hybrid andbipropellant compositions. The mode of employment of the fuels ofapplicants is also conventional which is, indeed, one of the significantadvantages residing in the present invention, as indicated above. Thus,if desired, they may be employed, for example, in the manner describedin US. Pats. 2,777,739 and 2,896,403.

One of the principal difficulties known to exist in the use ofmetal-based fuels known heretofore is the relatively slow rate at whichthe metallic elements oxidize in these standard fuel formulations. Thishas resulted in much of such fuels leaving the combustion chamber orarea unburned, thus greatly reducing their utility and value. By the useof internal oxidizers in the monopropellant formulations proposedherein, the oxidation or buming rate of the metals can be controlled togive the desired combustion and the need for external oxidizer issubstantially eliminated.

Thiscombination of oxidizer and propellant is most desirablyaccomplished where monopropellant compositions are desired, however, bysubstitution on the carbon, nitrogen, or phosphorus elements of thefuels of the invention, e.g. in the phosphine and/ or hydride moiety ofthe propellant coordination compound, of nitrate substituents andpreferably methyl nitrate for hydrogen or hydrocarbyl substituents; themethyl nitrate thus providing the necessary oxidizer to cause combustionand substantially complete oxidation of the coordinatioucomplexandparticularly the metallic portion thereof without the use of anexternal oxidizer, with consequent substantially complete utiliziationof the energy of the coordination complex and the metallic moietythereof.

If a portion of the required oxidizer is included in the formulation ofthe solid fuel complex and is insufficient to maintain combustion, thena liquid oxidizer, for example, nitric acid, could be metered into thecombustion chamber to initiate and continue combustion and maintenanceof a controlled firing rate.

The fuels thus formed have been found to exhibit, as noted above,properties which obviate the deficiencies of their individual components(e.g. phosphine and a hydride) while retaining their advantages. Thus,stored orprocessed according to standard procedures, these compounds arefound to be stable both to spontaneous pyrolysis and, hydrolysis,relatively non-toxic due to a reduced vapor pressure and capable ofstorage for prolongedperiods in the presence of atmospheric oxygen andmoisture without visible deterioration. The chemical stability oftheseicompounds is retained at temperatures well above those normallyencountered in storage, handling and processing; nor will theydissociate due to shock or the like.

Ini addition, the complexes herein described and prepared are manifestlyless expensive to produce over the boron-based fuels now receiving widecommercial application. At the same time, however, these compoundsconstitute fuels which adhere under conditions of use, such as, forexample, in combination with suitable oxidizers if desired, heats ofcombustion within the range of 6000 to 7000 British thermal units(B.t.u.) per pound thereof.

Illustrative of the combinations of propellant and oxidizer compositionswithin the purview of the present invention are berylliumborohydride-phosphine and ammonium perchlorate; lithium aluminumhydride-hydrazine and fuming. nitric acid; diborane-vinyl phosphine andliquid oxygen; magnesium hydride-dimethyl amine and tetranitromethane;aluminum borohydride-dimethyl hydrazine and gaseous fluorine; andaluminum hydrideethylehe imine .and hydrogen peroxide. As indicatedabove, a propellant compound such as diborane-tri (nitromethyl)phosphineoxidizes well in the absence of any additional oxidizer. As alsoindicated above, the production of energy in the form of thrust, heatand/or light by oxidation of these compositions as well as the othersdescribed herein is eftected in a standard manner and in any suitableand standard combustion chamber or area of an engine adapted for jet androcket propulsion.

The following examples are further illustrative of the invention.

EXAMPLE 1 Preparation of beryllium borohydride-phosphine complex To .asolution of 3.87 grams (0.1 mole) of beryllium borohydride dissolved in100 grams of tetrahydrofuran at 25 C. is passed phosphine gas (generatedfrom Al-P and water) until absorption is complete. The solvent,tetrahydrofuran, is easily removed by distillation at 50 C. and 30 mm.Hg absolute pressure, leaving the phosphineberyllium borohydridecoordination compound which is stable in moist air and is suitable foruse as a component of a rocket propellant or a jet engine fuel.

EXAMPLE 2 Preparation of pentaborane-phosphine complex Following theprocedure of Example 1, to 6.41 grams (0.1 mole) of pentaboranedissolved in grams of tetrahydrofuran is added phosphine gas untilabsorption at 25 C. is complete. After distilling off the solvent undervacuum, a stable coordination compound, pentaboranephosphine, remainswhich is a suitable component of a jet engine fuel or rocket propellant.

EXAMPLE 3 Preparation of lithium aluminum hydridephosphine complexFollowing the procedure of Example 1, phosphine gas is passed into asolution of 3.80 grams (0.1 mole) of lithium aluminum hydride intetrahydrofuran until one mole (3.4 grams) of phosphine has beenabsorbed. The product, after solvent removal, is the lithium aluminumhydride-phosphine complex which is stable in moist air, and is suitablefor use as a component of a jet engine fuel, or rocket propellant.

EXAMPLE 4 Preparation of diborane-vinyl phosphine complex EXAMPLE 5Preparation of magnesium borohydride-ethylene phosphine complexFollowing the procedure of Examples 1 and 4, to a solution of 5.40 grams(0.1 mole) of magnesium borohydride in 100 grams of tetrahydrofuran isadded 6.00 grams (0.1 mole) of ethylene phosphine. The product,magnesium borohydride-ethylene phosphine complex may be polymerized withtraces of acid to form stable polymers which, with other components andan oxidizer, may be used as a solid rocket propellant.

EXAMPLE 6 Preparation of beryllium hydride-dihydrogen phosphine nitratecomplex To a solution of 9.50 grams (0.1 mole) of dihydrogen phosphinenitrate in 100 grams of tetrahydrofuran at -10 C. is added 1.1 grams ofberyllium hydride (0.1 mole). The complex, beryllium hydride-dihydrogenphosphine nitrate, remaining after removal of the solvent under vacuumis a suitable component of a liquid or solid fuel in which a part of theoxidizer is furnished by the complex.

EXAMPLE 7 Preparation of aluminum hydride-tri(methylene nitrate)phosphine complex To a solution of 3.00 grams (0.1 mole) of aluminumhydride polymer dissolved in 100 grams of diethyl ether is added 25.91grams (0.1 mole) tri(methylene nitrate) phosphine at 25 C. The solventis removed by vacuum distillation leaving the stable aluminumhydride-tri- (methyl nitrate) phosphine complex which may be utilized ina solid rocket propellant formulation in which a part of the oxidizer iscontained in the complex.

EXAMPLE 8 Preparation of lithium aluminum hydride-dimethyl amine complexTo a solution of lithium aluminum hydride (LiAlH (3.8 grams, 0.1 mole)dissolved in 200 grams of tetrahydrofuran at 30 C., is added 4.5 grams(0.1 mole) of dimethyl amine. The mixture is allowed to warm to roomtemperature and is maintained at 26 C. for 96 hours, after which timethe solvent, tetrahydrofuran, is removed in vacuo to yield lithiumaluminum hydridedimethyl amine which evidences upon elemental analysis:

Element Found Theory Lithium 8. 27 8. 40 Aluminum 32. 91 32. 6 Carbon28. 23 28. 9 Nitrogen 17. 16. 9

EXAMPLE 9 Preparation of lithium aluminum hydride-hydrazine complex To asolution of lithium aluminum hydride (3.8 grams) dissolved in 200 gramsof tetrahydrofuran, there is added, at 30 C., 3.2 grams of hydrazine.The mixture is permitted to warm to room temperature and is maintainedat 26 C. for 96 hours, after which time the solvent is removed in vacuoto yield lithium aluminum hydridehydrazine in a substantiallyquantitative yield.

EXAMPLE 10 Preparation of aluminum borohydride-unsym. dimethylhydrazinecomplex Preparation of aluminum borohydride-monomethyl amine complex Toa solution of 7.2 grams of aluminum borohydride, Al(BH dissolved in 200grams of tetrahydrofuran, there is added 3.1 grams of monomethyl amineat C. The mixture is permitted to warm to room temperature and ismaintained at 26 C. for 72 hours, after which time the solvent,tetrahydrofuran, is removed in vacuo to result in a substantiallyquantitative yield of aluminum borohydride-monomethyl amine.

EXAMPLE 12 Preparation of aluminum borohydride-ethylene imine complex Toa solution of 7.2 grams of aluminum borohydride, Al(BH dissolved in 200grams of tetrahydrofuran, there is added 4.3 grams of ethylene imine at20 C. The mixture is permitted to warm to room temperature and ismaintained at 26 C. for 72 hours, after which time the solvent,tetrahydrofuran, is removed in vacuo to result in a substantiallyquantitative yield of aluminum borohydride-ethylene imine.

EXAMPLE 13 Preparation of aluminum borohydride-hydrazine complex To asolution of 7.2 grams of aluminum borohydride, Al(BH dissolved in 200grams of tetrahydrofuran, there is added 3.2 grams of hydrazine at 30 C.The

mixture is permitted to warm to room temperature and is maintained at 26C. for 72 hours, after which time the solvent, tetrahydrofuran, isremoved in vacuo to result in a substantially quantitative yield ofaluminum borohydride-hydrazine.

EXAMPLE 14 Preparation of pentaborane-ethylene imine complex In asimilar manner, to a solution of 6.4 grams of pentaborane B H dissolvedin 200 grams of tetrahydrofuran, there is added 4.3 grams of ethyleneimine. The product secured in substantially quantitative yield ispentaborane-ethylene imine.

EXAMPLE 15 Preparation of tetraborane-monovinyl amine complex In asimilar manner, to a solution of 5.4 grams of tetraborane, B H dissolvedin 200 grams of tetrahydrofuran, there is added 4.3 grams of monovinylamine. The product secured in substantially quantitative yield istetraborane-monovinyl amine.

EXAMPLE 16 Preparation of diborane-ethylene diamine complex In a similarmanner, to a solution of 2.8 grams of diborane, B H dissolved in 200grams of tetrahydrofuran, there is added 6.0 grams of ethylene diamine.The prod not secured in substantially quantitative yield isdiboraneethylene diamine.

EXAMPLE 17 Preparation of beryllium borohydride-acrylonitrile complex Ina similar manner, to a solution of 3.9 grams of beryllium borohydride,Be(BH dissolved in 200 grams of tetrahydrofuran, there is added 5.3grams of acrylonitrile. The product secured in substantiallyquantitative yield is beryllium borohydride-acrylonitrile.

EXAMPLE 18 Preparation of magnesium hydride-din1ethylamine complex In asimilar manner, to a solution of 2.63 grams of magnesium hydride, MgHdissolved in 200 grams of tetrahydrofuran, there is added 4.5 grams ofdimethyl amine. The product secured in substantially quantitative yieldis magnesium hydride-dimethyl amine.

EXAMPLE 19 Preparation of diborane-tri(nitromethyl) phosphine complex Ina similar manner, employing diborane and tri(nitromethyl) phosphine,there is prepared the coordination compound,diborane-tri(nitromethyl)phosphine.

EXAMPLE 20 Preparation of aluminum hydride-ethylene imine complex In asimilar manner to that described in the foregoing examples, there isprepared, employing aluminum hydride and ethylene imine as thereactants, the coordination compound, aluminum hydride-ethylene imine.

What is claimed is:

1. A coordination compound composed of a trivalent phosphorus compoundas an electron donor compound and an electron acceptor compound selectedfrom the group consisting of a metal hydride and a correspondingborohydride and organo metallic constituent of said metal wherein themetal is selected from the group consisting of beryllium, lithium,magnesium, sodium, calcium, aluminum and potassium.

2. The coordination compound beryllium borohydridephosphine.

3. The coordination compound lithium aluminum hydride-phosphine.

4. The coordination compound diborane-vinyl phosphine.

5. The coordination compound magnesium borohydride-ethylene phosphine.

6. The coordination compound beryllium hydride-di hydrogen phosphinenitrate.

7. The coordination compound aluminum hydride-tri (methylene nitrate)phosphine.

8.1'The coordination compound lithium aluminum hydride-dimethyl amine.

9. The coordination compound lithium aluminum hydride-hydrazine.

10. The coordination compound aluminum dride-dimethylhydrazine.

11. The coordination compound aluminum dride-monomethyl amine.

12. The coordination compound aluminum dride-ethylene imine.

13. Theqcoordination compound aluminum dride-hydrazine.

14. The coordination compound pentaborane-ethylene mine.

15. The coordination compound tetraborane-monovinyl amine.

16.; The coordination compound diborane-ethylene diamine.

borohyborohyborohyborohy- References Cited UNITED STATES PATENTS 9/1967Hogsett et al. 149-22 XR 5/1964 Knight 149-36 XR OTHER REFERENCES Ramseyet al.: Nature, vol. 190, May 6, 1961, pp. 528 and 529.

Chatt et al.: J. Chem. Soc. (London), 1959, pp. 4021 and 4026 to 4031.

LELAND A. SEBASTIAN, Primary Examiner US. Cl. X.R.

1. A COORDINATION COMPOUND COMPOSED OF A TRIVALENT PHOSPHORUS COMPOUNDAS AN ELECTRON DONOR COMPOUND AND AN ELECTRON ACCEPTOR COMPOUND SELECTEDFROM THE GROUP CONSISTING OF A METAL HYDRIDE AND A CORRESPONDINGBOROHYDRIDE AND ORGANO METALLIC CONSTITUENT OF SAID METAL WHEREIN THEMETAL IS SELECTED FROM THE GROUP CONSISTING OF BERYLLIUM, LITHIUM,MAGNESIUM, SODIUM, CALCIUM, ALUMINUM AND POTASSIUM.
 9. THE COORDINATIONCOMPOUND LITHIUM ALUMINUM HYDRIDE-HYDRAZINE.